US5272205A - Polymer mixtures of high ageing resistance - Google Patents

Polymer mixtures of high ageing resistance Download PDF

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Publication number
US5272205A
US5272205A US07/435,056 US43505689A US5272205A US 5272205 A US5272205 A US 5272205A US 43505689 A US43505689 A US 43505689A US 5272205 A US5272205 A US 5272205A
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weight
parts
styrene
graft
acrylonitrile
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US07/435,056
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Herbert Eichenauer
Alfred Pischtschan
Christian Lindner
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Bayer AG
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Bayer AG
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Assigned to BAYER AKTIENGESELLSCHAFT reassignment BAYER AKTIENGESELLSCHAFT ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: EICHENAUER, HERBERT, LINDNER, CHRISTIAN, PISCHTSCHAN, ALFRED
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C08L51/085—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds on to polysiloxanes

Definitions

  • This invention relates to polymer alloys having high weathering and ageing resistance, good processing properties and high strength at low temperatures.
  • Polymer alloys of high ageing resistance include, for example, graft polymers based on crosslinked acrylate rubbers in combination with a thermoplastic resin , so-called ASA polymers (cf. for example DE-AS 12 60 135, DE-OS 19 11 882, DE-OS 28 26 925, EP-A-71 098) and graft polymers based on ethylene/propylene/diene rubbers (EPDM rubbers) in combination with a thermoplastic resin, so-called AES polymers (cf. for example DE-OS 28 30 232, DE-OS 30 01 766, EP-A 121 327, EP-A-134 154).
  • ASA polymers cf. for example DE-AS 12 60 135, DE-OS 19 11 882, DE-OS 28 26 925, EP-A-71 098
  • EPDM rubbers graft polymers based on ethylene/propylene/diene rubbers
  • AES polymers cf. for example DE-OS 28 30 232, DE-OS 30 01
  • thermoplastic polymer alloys combining very high weathering resistance with high strength at low temperatures are obtained when ASA systems, in which the rubber phase has a special particle size, are combined with graft products based on silicone rubber having a special particle size.
  • the resulting thermoplastic polymer alloys are also distinguished by improved processing properties.
  • the present invention relates to thermoplastic molding compounds of A) 5 to 95% by weight and preferably 20 to 80% by weight of a graft product of a mixture of 50 to 100 parts by weight and preferably 60 to 95 parts by weight styrene, ⁇ -methyl styrene, vinyl toluene, preferably p-methyl styrene, methyl methacrylate or mixtures thereof and 0 to 50 parts by weight and preferably 5 to 40 parts by weight acrylonitrile on a particulate silicone rubber with a mean particle diameter (d 50 ) of from 0.10 to 0.50 ⁇ m and preferably from 0.10 to 0.15 ⁇ m or from 0.25 to 0.50 ⁇ m having a total rubber content of from 30 to 90% by weight and preferably from 40 to 80% by weight and B) 95 to 5% by weight and preferably 80 to 20% by weight of a graft product of a mixture of 50 to 100 parts by weight and preferably 60 to 95 parts by weight styrene, ⁇ -methyl
  • the graft products based on silicone rubber which may be used in the production of the molding compounds according to the invention are obtained by radical polymerization of vinyl monomers or mixtures of vinyl monomers in the presence of silicone rubber, more especially in the presence of silicone rubber in emulsion form, the monomers being at least partly grafted onto the rubber (graft polymerization).
  • Suitable vinyl monomers are, for example, styrene, nucleus- or side-chain-substituted styrenes, more especially p-methyl styrene and ⁇ -methyl styrene, halogen-substituted styrenes, for example chlorostyrene or bromo-styrene, vinyl naphthalene, derivatives of ⁇ , ⁇ -unsaturated mono- or dicarboxylic acids, more especially C 1-5 alkyl esters of acrylic or methacrylic acid, preferably methyl methacrylate, or the nitriles of acrylic acid or methacrylic acid, maleic anhydride, N-phenyl maleic imide or mixtures thereof.
  • a preferred monomer mixture is a combination of styrene and/or ⁇ -methyl styrene and acrylonitrile, preferably in a ratio by weight of styrene and/or ⁇ -methyl styrene to acrylonitrile of 1:1 to 10:1.
  • Suitable silicone rubbers are, for example, the compounds described in DE-OS 36 29 763 which consist essentially of chemically linked siloxane groups corresponding to the formulae R 2 SiO, RSiO 3/2 , R 2 R 3 SiO 1/2 , SiO 4/2 , R 1 CH ⁇ CH--(R 2 )-- and H--S--, where R is a monofunctional, saturated hydrocarbon radical, more especially CH 3 , phenyl, C 2 H 5 , optionally substituted by SH, halogen, C 1-6 oxyalkyl, R 1 is H, C 1-6 alkyl, more especially H, CH 3 , R 2 is a single bond, C 1-4 alkylene, more especially --CH 2 --, --C 2 H 4 --, a single bond and R 3 has the same meaning as R or represents OH, the quantities of the individual siloxane units being gauged in such a way that 0 to 0.5 mol units R 2 R 3 SiO 1/2 , 0 to 10 mol units of the formula
  • silicone rubbers have core/shell structure; for example particulate silicone rubbers surrounded by a shell of crosslinked acrylate rubber (cf. DE-OS 36 17 267) or particulate silicone rubbers containing a core of crosslinked acrylate rubber (cf. DE-OS 37 20 475) or of a styrene/acrylonitrile copolymer (cf. DE-OS 37 20 476).
  • the graft products based on silicone rubbers (A) are preferably produced by emulsion polymerization using at least partly crosslinked silicone rubbers present in emulsion form as the graft base.
  • the graft polymerization may be carried out by known methods and is preferably carried out at temperatures of 30° C. to 100° C. using radical initiators, for example organic or inorganic peroxides, inorganic persulfates, for example potassium persulfate, azo initiators, for example azo-bis-isobutyronitrile, and redox systems consisting of an oxidizing agent, preferably a peroxide, and a reducing agent and optionally with addition of an aqueous emulsifier solution (for example anionic or nonionic emulsifier components, preferably sodium, potassium or ammonium salts of long-chain carboxylic acids containing 10 to 20 carbon atoms, for example potassium oleate, alkyl sulfates containing 10 to 20 carbon atoms, alkyl sulfonates containing 10 to 20 carbon atoms or alkali or ammonium salts of disproportionated abietic acid).
  • radical initiators for example organic or inorganic peroxid
  • the graft products based on silicone rubbers have a rubber content of 30 to 90% by weight and preferably 40 to 80% by weight.
  • the mean particle diameters (d 50 values) of the silicone rubber component are from 0.10 to 0.50 ⁇ m and preferably from 0.10 to 0.15 ⁇ m and from 0.25 to 0.50 ⁇ m.
  • the graft products based on acrylate rubber (B) which are used for the production of the molding compounds according to the invention are obtained by radical polymerization of vinyl monomers or mixtures of vinyl monomers in the presence of acrylate rubber, the monomers being at least partly polymerized onto the rubber.
  • Suitable vinyl monomers are, for example, styrene, ⁇ -methyl styrene, nucleus-substituted styrenes, such as p-methyl styrene, C 1-5 alkyl esters of acrylic or methacrylic acid, preferably methyl methacrylate, maleic anhydride, N-phenyl maleic imide or mixtures thereof.
  • the preferred monomer mixture is a combination of styrene and/or ⁇ -methyl styrene and acrylonitrile, preferably in a ratio by weight of ( ⁇ -methyl) styrene to acrylonitrile of 1:1 to 10:1.
  • Suitable acrylate rubbers are, for example, polymers based on C 1-5 alkyl acrylates (for example methyl, butyl, octyl or 2-ethylhexyl acrylate), optionally in admixture with up to 40% by weight other vinyl monomers.
  • Polyfunctional monomers are copolymerized to crosslink the acrylate rubbers.
  • polyfunctional monomers are esters of unsaturated carboxylic acids with a polyol (preferably 2 to 20 carbon atoms in the ester group), such as ethylene glycol dimethacrylate, esters of a polybasic carboxylic acid with an unsaturated alcohol (preferably 8 to 30 carbon atoms in the ester group), such as triallyl cyanurate, triallyl isocyanurate; divinyl compounds, such as divinyl benzene; esters of unsaturated carboxylic acids with unsaturated alcohols (preferably 6 to 12 carbon atoms in the ester group), such as allyl methacrylate; phosphoric acid esters, for example triallyl phosphate and 1,3,5-triacryloylhexahydro-s-triazine.
  • esters of unsaturated carboxylic acids with a polyol preferably 2 to 20 carbon atoms in the ester group
  • esters of a polybasic carboxylic acid with an unsaturated alcohol preferably 8 to 30 carbon atom
  • Particularly preferred polyfunctional monomers are triallyl cyanurate, triallyl isocyanurate, triallyl phosphate, allyl methacrylate, ethylene glycol dimethacrylate and 1,3,5-triacryloylhexahydro-s-triazine.
  • the quantity of the polyfunctional monomers used for crosslinking is preferably from 0.05 to 10% by weight and more preferably from 0.1 to 5.0% by weight (based on the total quantity of crosslinked acrylate rubber).
  • Other suitable acrylate rubber components are compounds of the so-called core/shell type, such as for example particulate acrylate rubbers containing a core of crosslinked polybutadiene (cf. EP-P 34 748).
  • the graft products based on acrylate rubbers are preferably produced by emulsion polymerization, at least partly crosslinked acrylate rubbers present in emulsion form being used as the graft base.
  • the graft polymerization may be carried out by known methods and is preferably carried out at temperatures in the range from 30° to 100° C. using radical initiators, for example organic or inorganic peroxides, inorganic persulfates, for example potassium persulfate, azo initiators, for example azo-bis-isobutyronitrile, and redox systems consisting of an oxidizing agent, preferably a peroxide, and a reducing agent and optionally with addition of an aqueous emulsifier solution (for example anionic or non-ionic emulsifier components, preferably sodium, potassium or ammonium salts of long-chain carboxylic acids containing 10 to 20 carbon atoms, for example potassium oleate, alkyl sulfates containing 10 to 20 carbon atoms, alkyl sulfonates containing 10 to 20 carbon atoms or alkali or ammonium salts of disproportionated abietic acid).
  • radical initiators for example organic or inorganic
  • the graft products based on acrylate rubbers have a rubber content of 30 to 80% by weight and preferably 40 to 75% by weight.
  • the mean particle diameters (d 50 values) of the acrylate rubber are from 0.05 to 1.00 ⁇ m, preferably from 0.08 to 0.15 ⁇ m or from 0.30 to 0.60 ⁇ m.
  • the molding compounds according to the invention may be produced by mixing their constituents A) and B) with one another at relatively high temperatures, more especially at 100° C. to 280° C., for example in kneaders, on roll stands or in screw extruders.
  • A) and B) are obtained in the form of suspensions, solutions or emulsions, they may be mixed and worked up together.
  • Typical additives such as antioxidants, lubricants, flameproofing agents, fillers, pigments, antistatic agents, may be added in typical quantities to the molding compounds.
  • the mixtures according to the invention are ageing-resistant thermoplastic molding compounds combining high strength at low temperatures with good processibility where they are processed by extrusion, calendering and injection molding. They may be processed to ageing-resistant moldings, although they are also suitable as modifiers for other plastics, more especially for brittle vinyl monomer resins, such as styrene/acrylonitrile copolymers (SAN resins), ⁇ -methyl styrene/acrylonitrile copolymers, polystyrene, polymethyl methacrylate, polyvinyl chloride.
  • SAN resins styrene/acrylonitrile copolymers
  • ⁇ -methyl styrene/acrylonitrile copolymers polystyrene, polymethyl methacrylate, polyvinyl chloride.
  • a particularly preferred mixture of this type consists of 5 to 80% by weight and preferably 10 to 70% by weight of the mixture according to the invention and 95 to 20% by weight and preferably 90 to 30% by weight of a thermoplastic resin of 5 to 40 parts by weight acrylonitrile and 95 to 60 parts by weight styrene, ⁇ -methyl styrene, p-methyl styrene, methyl methacrylate or mixtures thereof.
  • SAN resins These resins are known. They are often referred to as SAN resins. They may be combined with the mixture of the graft polymers by adding them during mixing of the graft polymers.
  • the resins must be present in the same physical form (solid, latex, solution) as the graft polymers. It is also possible to mix solid resins with prepared mixtures of the graft polymers or successively with the two graft polymer components in internal mixers and extruders.
  • particle size always means the mean particle diameter d 50 as determined by ultracentrifuge measurements in accordance with W. Scholtan et al., Kolloid-Z. u. Z. Polymere 250 (1972), 782-796.
  • the silicone rubber emulsion is prepared as follows: 38.4 parts by weight octamethyl cyclotetrasiloxane, 1.2 parts by weight tetramethyl tetravinyl cyclotetrasiloxane and 1 part by weight ⁇ -mercaptopropyl methyl dimethoxysilane are stirred with one another. 1.00 Part by weight dodecyl benzene sulfonic acid are then added, followed by the introduction over a period of one hour with intensive stirring of 58.4 parts by weight water.
  • the pre-emulsion is homogenized twice at approximately 220 bar in a high-pressure emulsifying machine.
  • dodecyl benzene sulfonic acid Another 0.5 part by weight dodecyl benzene sulfonic acid are then added. The emulsion is stirred for two hours at 85° C. and then for 36 hours at room temperature. It is neutralized using 5 N NaOH. A stable emulsion having a solids content of approximately 36% is obtained; the mean particle diameter (d 50 ) is 135 nm.
  • the silicone rubber emulsion was prepared in the same way as described in A), except that 0.90 part by weight dodecyl benzene sulfonic acid was used and the pressure in the homogenizing step was approximately 190 bar.
  • the grafting reaction was carried out as described in A).
  • Production comprised the following steps:
  • a solution of 3 parts by weight potassium peroxodisulfate in 100 parts by weight water is introduced into the reactor at 70° C.
  • the following solutions are then introduced into the reactor over a period of 5 hours at 70° C.:
  • the latex formed contains the polymer in a concentration of 35% by weight.
  • the polymer consists of 70% by weight silicone rubber and 30% by weight acrylate rubber.
  • n-butyl acrylate and 0.5 part by weight triallyl cyanurate are added over a period of 4 hours to a solution of 3 parts by weight of the sodium salt of C 9-18 alkyl sulfonic acids and 0.75 part by weight potassium persulfate in 150 parts by weight water, the temperature being adjusted to 65° C. Following an after-reaction of 2 hours at 65° C., a 40% latex having a mean particle diameter (d 50 ) of approximately 100 nm is obtained.
  • a graft latex having a solids content of 33% is obtained, being converted into the graft product in the form of a white powder by coagulation with an aqueous magnesium sulfate/ acetic acid solution, filtration and drying in vacuo.
  • a core/shell acrylate rubber having a solids content of 35% and a mean particle size (d 50 ) of 480 nm is obtained.
  • a graft latex having a solids content of 33% is obtained, being converted into the graft product in the form of a white powder by coagulation with an aqueous magnesium sulfate/acetic acid solution, filtration and drying in vacuo.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
US07/435,056 1988-11-24 1989-11-13 Polymer mixtures of high ageing resistance Expired - Fee Related US5272205A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3839585 1988-11-24
DE3839585A DE3839585A1 (de) 1988-11-24 1988-11-24 Polymermischungen mit guter alterungsbestaendigkeit

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US5272205A true US5272205A (en) 1993-12-21

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US (1) US5272205A (de)
EP (1) EP0370346B1 (de)
JP (1) JPH0320348A (de)
DE (2) DE3839585A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932655A (en) * 1997-11-19 1999-08-03 Bayer Corporation Weatherable resinous composition having improved opacity and impact strength
US20060183858A1 (en) * 2003-03-28 2006-08-17 Kentaro Takesada Acrylic elastomer composition
US20150119489A1 (en) * 2013-10-25 2015-04-30 Samsung Sdi Co., Ltd. Thermoplastic Resin Composition Having Excellent Colorability and Mechanical and Physical Properties

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY107915A (en) * 1990-12-11 1996-06-29 Claymax Corp Clay liner for steep slopes
DE4141319A1 (de) * 1991-12-14 1993-10-14 Roehm Gmbh Hochschlagzähe Polymermischungen
JP3163180B2 (ja) * 1992-10-05 2001-05-08 三菱レイヨン株式会社 耐衝撃性樹脂組成物
JP3168078B2 (ja) * 1992-10-09 2001-05-21 三菱レイヨン株式会社 耐衝撃性樹脂組成物
US6169149B1 (en) * 1998-12-04 2001-01-02 General Electric Company Emulsion polymerized silicone-acrylate rubber impact modifiers thermoplastic blends, and methods for making
JP7106880B2 (ja) * 2018-02-08 2022-07-27 テクノＵｍｇ株式会社 熱可塑性樹脂組成物およびその成形品

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2547508A1 (de) * 1974-10-21 1976-04-22 Japan Synthetic Rubber Co Ltd Aeusserst wetterfestes, warmformbares folienmaterial
EP0154244A2 (de) * 1984-02-27 1985-09-11 Bayer Ag Matte Formmassen
EP0220160A2 (de) * 1985-10-24 1987-04-29 Monsanto Company Schlag- und wetterzähe thermoplastische Zusammensetzungen
EP0249964A2 (de) * 1986-06-17 1987-12-23 Mitsubishi Rayon Co., Ltd. Polykarbonatharz-Zusammensetzung
EP0260552A2 (de) * 1986-09-11 1988-03-23 Mitsubishi Rayon Co., Ltd. Pfropfcopolymerisat und dieses enthaltende Polyphenylenetherharzzusammensetzung.
US4806593A (en) * 1986-09-17 1989-02-21 Bayer Aktiengesellschaft Thermoplastic moulding materials having good resistance to ageing and good low-temperature impact strength
US4916186A (en) * 1985-10-24 1990-04-10 Monsanto Company Impact- and weather-resistant thermoplastic polyblends

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2547508A1 (de) * 1974-10-21 1976-04-22 Japan Synthetic Rubber Co Ltd Aeusserst wetterfestes, warmformbares folienmaterial
US4042548A (en) * 1974-10-21 1977-08-16 Japan Synthetic Rubber Company Limited Highly weather-resistant, thermoformable sheeting
EP0154244A2 (de) * 1984-02-27 1985-09-11 Bayer Ag Matte Formmassen
US4652614A (en) * 1984-02-27 1987-03-24 Bayer Aktiengesellschaft Mat moulding materials
EP0220160A2 (de) * 1985-10-24 1987-04-29 Monsanto Company Schlag- und wetterzähe thermoplastische Zusammensetzungen
US4916186A (en) * 1985-10-24 1990-04-10 Monsanto Company Impact- and weather-resistant thermoplastic polyblends
EP0249964A2 (de) * 1986-06-17 1987-12-23 Mitsubishi Rayon Co., Ltd. Polykarbonatharz-Zusammensetzung
EP0260552A2 (de) * 1986-09-11 1988-03-23 Mitsubishi Rayon Co., Ltd. Pfropfcopolymerisat und dieses enthaltende Polyphenylenetherharzzusammensetzung.
US4806593A (en) * 1986-09-17 1989-02-21 Bayer Aktiengesellschaft Thermoplastic moulding materials having good resistance to ageing and good low-temperature impact strength

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Derwent Abstract of J47030751, "Thermoplastic Resin Compsns-of Good Impact Resistance and Weather Resistance."
Derwent Abstract of J47030751, Thermoplastic Resin Compsns of Good Impact Resistance and Weather Resistance. *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5932655A (en) * 1997-11-19 1999-08-03 Bayer Corporation Weatherable resinous composition having improved opacity and impact strength
US20060183858A1 (en) * 2003-03-28 2006-08-17 Kentaro Takesada Acrylic elastomer composition
US7449521B2 (en) * 2003-03-28 2008-11-11 Kaneka Corporation Acrylic elastomer composition
US20150119489A1 (en) * 2013-10-25 2015-04-30 Samsung Sdi Co., Ltd. Thermoplastic Resin Composition Having Excellent Colorability and Mechanical and Physical Properties
US9416266B2 (en) * 2013-10-25 2016-08-16 Samsung Sdi Co., Ltd. Thermoplastic resin composition having excellent colorability and mechanical and physical properties

Also Published As

Publication number Publication date
EP0370346A3 (en) 1990-11-14
EP0370346B1 (de) 1993-01-07
DE58903229D1 (de) 1993-02-18
JPH0320348A (ja) 1991-01-29
DE3839585A1 (de) 1990-05-31
EP0370346A2 (de) 1990-05-30

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